Triazinone derivative containing sulfonyl structure and preparation method therefor, and insecticidal and bactericidal uses thereof

专利详情

标题Triazinone derivative containing sulfonyl structure and preparation method therefor, and insecticidal and bactericidal uses thereof

[标]当前申请(专利权)人南开大学

申请日2017年9月21日

申请号EP2017892064

公开(公告)日2019年12月11日

公开(公告)号EP3486237B1

授权日-

法律状态/事件授权

专利类型授权发明

发明人WANG, QINGMIN | SONG, HONGJIAN | YANG, YAN | LIU, YUXIU | WANG, ZIWEN

受理局欧洲专利局

当前申请人(专利权)地址No. 94 Weijin Road Nankai District, Tianjin, CN

IPC分类号C07D253/06 | A01N43/707

国民经济行业分类号C2614 | C2653 | C3521 | C2663 | C2684 | C2661

代理机构MARTEGANI, FRANCO

代理人-

被引用专利数量-

专利价值$ 410,000

摘要

The present invention belongs to the technical field of pesticides, particularly relates to sulfonyl-structure-containing triazinone derivatives, their preparation methods, and their uses in insect killing and/or bacterium killing. The sulfonyl-structure-containing triazinone derivatives are compounds represented by formula (Ia) or (Ib). The sulfonyl-structure-containing triazinone derivatives provided in the present invention exhibit outstanding insecticidal activity as well as bactericidal activity.

1. A sulfonyl-structure-containing triazinone derivative, which is a compound represented by formula (Ia): wherein R1 is C1-C12 alkyl, C3-C6 cycloalkyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted benzyl, substituted or unsubstituted phenethyl, substituted or unsubstituted phenylpropyl, substituted or unsubstituted phenylbutyl, nitrogen-containing heterocycle containing 1-10 carbon atoms, oxygen-containing heterocycle containing 1-10 carbon atoms, or sulfur-containing heterocycle containing 1-10 carbon atoms; the substituents of the substituted phenyl, the substituted naphthyl, the substituted benzyl, the substituted phenethyl, substituted phenylpropyl, and the substituted phenylbutyl are one or more substituents respectively and independently selected from the group consisted of hydroxyl, halogen, cyano, nitro, ester, trifluoromethyl, trifluoromethoxy, amido, C1-C6 alkyl, C1-C6 alkoxy, carbonyloxy substituted by C1-C4 alkyl, andcarbonyloxy substituted by C1-C4 alkoxy.

2. The triazinone derivative according to claim 1, wherein the R1 is C1-C8 alkyl, C3-C6 cycloalkyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted benzyl, substituted or unsubstituted phenethyl, substituted or unsubstituted phenylpropyl, substituted or unsubstituted phenylbutyl, nitrogen-containing heterocycle containing 2-8 carbon atoms, oxygen-containing heterocycle containing 2-8 carbon atoms, or sulfur-containing heterocycle containing 2-8 carbon atoms; the substituents of the substituted phenyl, the substituted naphthyl, the substituted benzyl, the substituted phenethyl, the substituted phenylpropyl, and the substituted phenylbutyl are one or more substituents respectively and independently selected from the group consisted of hydroxyl, F, Cl, Br, I, cyano, nitro, -COOCH3, -COOCH2CH3, trifluoromethyl, trifluoromethoxy, -NH-CO-CH3, -NH-CO-CH2CH3, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, C1-C5 alkyl, C1-C5 alkoxy, -O-CO-CH3, -O-CO-CH2CH3, -O-CO-O-CH3, and -O-CO-O-CH2CH3.

3. The triazinone derivative according to claim 1 or 2, wherein the compound represented by formula (Ia) is at least one of the compounds represented by the following formulae: Ia-1 Ia-2 Ia-3 Ia-4 Ia-5 Ia-6 Ia-7 Ia-8 Ia-9 Ia-10 Ia-11 Ia-12 Ia-13 Ia-14 Ia-15 Ia-16 Ia-17 Ia-18 Ia-19 Ia-20 Ia-21 Ia-22 Ia-23 Ia-24 Ia-25 Ia-26 Ia-27 Ia-28 Ia-29 Ia-30 Ia-31 Ia-32 Ia-33 Ia-34

4. A method for preparing the triazinone derivative according to any of claims 1-3, comprising: controlling amino-triazinone represented by formula (II) and sulfonyl chloride compound represented by formula (III) to have a substitution reaction in an organic solvent in the presence of an acid binding agent to obtain a compound represented by formula (Ia);

5. The method according to claim 4, wherein the molar ratio of the amino-triazinone represented by formula (II) to the sulfonyl chloride compound represented by formula (III) is 1:0.8-1.2, preferably is 1:1-1.1; preferably, the acid binding agent is at least one of the agents selected from the group consisted of sodium carbonate, potassium carbonate, cesium carbonate, triethylamine, and pyridine; preferably, the organic solvent is at least one of the solvents selected from the group consisted of methanol, ethanol, pyridine, N,N-dimethyl formamide and dimethyl sulfoxide; preferably, the organic solvent is dosed so that the concentration of the amino-triazinone represented by formula (II) is 0.05-0.5mmol/mL.

6. The method according to claim 4 or 5, wherein the conditions of the substitution reaction include: temperature: 15-40°C; time: 4-12h.

7. A sulfonyl-structure-containing triazinone derivative, which is a compound represented by formula (Ib): wherein each R1 is respectively and independently selected from the group consisted of C1-C2 alkyl, C3-C6 cycloalkyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted benzyl, substituted or unsubstituted phenethyl, substituted or unsubstituted phenylpropyl, substituted or unsubstituted phenylbutyl, nitrogen-containing heterocycle containing 1-10 carbon atoms, oxygen-containing heterocycle containing 1-10 carbon atoms, or sulfur-containing heterocycle containing 1-10 carbon atoms; the substituents of the substituted phenyl, the substituted naphthyl, the substituted benzyl, the substituted phenethyl, the substituted phenylpropyl, and the substituted phenylbutyl are one or more substituents respectively and independently selected from the group consisted of hydroxyl, halogen, cyano, nitro, ester, trifluoromethyl, trifluoromethoxy, amido, C1-C6 alkyl, C1-C6 alkoxy, carbonyloxy substituted by C1-C4 alkyl, and carbonyloxy substituted by C1-C4 alkoxy.

8. The triazinone derivative according to claim 7, wherein each R1 is respectively and independently selected from the group consisted of C1-C8 alkyl, C3-C6 cycloalkyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted benzyl, substituted or unsubstituted phenethyl, substituted or unsubstituted phenylpropyl, substituted or unsubstituted phenylbutyl, nitrogen-containing heterocycle containing 2-8 carbon atoms, oxygen-containing heterocycle containing 2-8 carbon atoms, and sulfur-containing heterocycle containing 2-8 carbon atoms; the substituents of the substituted phenyl, the substituted naphthyl, the substituted benzyl, the substituted phenethyl, the substituted phenylpropyl, and the substituted phenylbutyl are one or more substituents respectively and independently selected from the group consisted of hydroxyl, F, Cl, Br, I, cyano, nitro, -COOCH3, -COOCH2CH3, trifluoromethyl, trifluoromethoxy, -NH-CO-CH3, -NH-CO-CH2CH3, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, C1-C5 alkyl, C1-C5 alkoxy, -O-CO-CH3, -O-CO-CH2CH3, -O-CO-O-CH3, and -O-CO-O-CH2CH3.

9. The triazinone derivative according to claim 7 or 8, wherein the compound represented by formula (Ib) is at least one of the compounds represented by the following formulae: Ib-1 Ib-2 Ib-3 Ib-4 Ib-5 Ib-6 Ib-7 Ib-8 Ib-9

10. A method for preparing the triazinone derivative according to any of claims 7-9, comprising: controlling amino-triazinone represented by formula (II) and sulfonyl chloride compound represented by formula (III) to have a substitution reaction in an organic solvent in the presence of an acid binding agent to obtain a compound represented by formula (Ib);

11. The method according to claim 10, wherein the molar ratio of the amino-triazinone represented by formula (II) to the sulfonyl chloride compound represented by formula (III) is 1:1.8-2.5, preferably is 1:2-2.4; preferably, the acid binding agent is at least one of the agents selected from the group consisted of sodium carbonate, potassium carbonate, cesium carbonate, triethylamine, and pyridine; preferably, the organic solvent is at least one of the solvents selected from the group consisted of methanol, ethanol, pyridine, N,N-dimethyl formamide and dimethyl sulfoxide; preferably, the organic solvent is dosed so that the concentration of the amino-triazinone represented by formula (II) is 0.05-0.5mmol/mL.

12. The method according to claim 10 or 11, wherein the conditions of the substitution reaction include: temperature: 15-40°C; time: 4-12h.

13. Use of the triazinone derivative according to any of claims 1-3 and 7-9 in insect killing and/or bacterium killing.

14. The use according to claim 13, wherein the insect is at least one of aphides, mosquito larvae, cotton bollworms, maize borers, and armyworms; and wherein the bacterium is at least one of the pathogenic bacteria that may cause tomato early blight, wheat head blight, potato late blight, capsicum phytophthora blight, sclerotinia rot of colza, cucumber gray mold, rice sheath blight, cucumber fusarium wilt, cercospora brown spot of peanut, apple ring rot, wheat sheath blight, corn southern leaf blight, watermelon anthracnose, and rice bakanae disease.

FIELD OF THE INVENTION

[0001]The present invention belongs to the technical field of pesticides, particularly relates to sulfonyl-structure-containing triazinone derivatives, their preparation methods, and their uses in insect killing and/or bacterium killing.

BACKGROUND OF THE INVENTION

[0002]Pymetrozine is a new heterocyclic insecticide discovered by Ciba-Geigy in 1988, whose characteristics including unique action, high selectivity, free of cross-resistance compared with conventional insecticides, and environmental safety, etc., and can attain a unique prevention and control effect against pests with piercing-sucking mouthpart, especially against aphides. Therefore, since pymetrozine emerged, it has been widely applied in prevention and control of aphides, whiteflies, and black-tailed leafhoppers for field crops and ornamental plants. However, owing to the unique action of pymetrozine, there are only three commercial insecticide products in this category up to now, i.e., pymetrozine, R-768 and pyrifluquinazon. Summarized on the basis of literatures, it is found that the researches on these insecticides mainly focus on triazinone ring and pyridine ring; however, there is no report on utilization of sulfone or sulfoxide as common active groups in the molecular designs of medicines and pesticides. As more and more attentions are paid to environmental protection all over the world, it is an urgent task to develop efficient, low-toxic, and environmentally friendly insecticides in the pymetrozine category in present agricultural production.

SUMMARY OF THE INVENTION

[0003]The object of the present invention is to provide sulfonyl-structure-containing triazinone derivatives, their preparation methods, and their uses in insect killing and/or bacterium killing. The sulfonyl-structure-containing triazinone derivatives in this patent application exhibit outstanding insecticidal activity as well as bactericidal activity.

[0004]In a first aspect, the present invention provides a sulfonyl-structure-containing triazinone derivative, which is a compound represented by formula (I a ): wherein R 1< is C1-C12 alkyl, C3-C6 cycloalkyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted benzyl, substituted or unsubstituted phenethyl, substituted or unsubstituted phenylpropyl, substituted or unsubstituted phenylbutyl, nitrogen-containing heterocycle containing 1-10 carbon atoms, oxygen-containing heterocycle containing 1-10 carbon atoms, or sulfur-containing heterocycle containing 1-10 carbon atoms; the substituents of the substituted phenyl, the substituted naphthyl, the substituted benzyl, the substituted phenethyl, the substituted phenylpropyl, and the substituted phenylbutyl are one or more substituents respectively and independently selected from the group consisted of hydroxyl, halogen, cyano, nitro, ester group, trifluoromethyl, trifluoromethoxy, amido, C1-C6 alkyl, C1-C6 alkoxy, carbonyloxy substituted by C1-C4 alkyl, or carbonyloxy substituted by C1-C4 alkoxy.

[0005]In a second aspect, the present invention provides a preparation method of the above-mentioned triazinone derivative, which comprises: controlling amino-triazinone represented by formula (II) and sulfonyl chloride compound represented by formula (III) to have a substitution reaction in an organic solvent in the presence of an acid binding agent to obtain a compound represented by formula (I a );

[0006]In a third aspect, the present invention provides a sulfonyl-structure-containing triazinone derivative, which is a compound represented by formula (I b ): wherein each R 1< is respectively and independently selected from the group consisted of C1-C2 alkyl, C3-C6 cycloalkyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted benzyl, substituted or unsubstituted phenethyl, substituted or unsubstituted phenylpropyl, substituted or unsubstituted phenylbutyl, nitrogen-containing heterocycle containing 1-10 carbon atoms, oxygen-containing heterocycle containing 1-10 carbon atoms, and sulfur-containing heterocycle containing 1-10 carbon atoms; the substituents of the substituted phenyl, the substituted naphthyl, the substituted benzyl, the substituted phenethyl, the substituted phenylpropyl, and the substituted phenylbutyl are one or more substituents respectively and independently selected from the group consisted of hydroxyl, halogen, cyano, nitro, ester group, trifluoromethyl, trifluoromethoxy, amido, C1-C6 alkyl, C1-C6 alkoxy, carbonyloxy substituted by C1-C4 alkyl, and carbonyloxy substituted by C1-C4 alkoxy.

[0007]In a fourth aspect, the present invention provides a preparation method of the above-mentioned triazinone derivative, which comprises: controlling amino-triazinone represented by formula (II) and sulfonyl chloride compound represented by formula (III) to have a substitution reaction in an organic solvent in the presence of an acid binding agent to obtain a compound represented by formula (I b );

[0008]In a fifth aspect, the present invention provides a use of the above-mentioned triazinone derivative in insect killing.

[0009]In a sixth aspect, the present invention provides a use of the above-mentioned triazinone derivative in bacterium killing.

[0010]The triazinone derivatives provided in the present invention exhibit outstanding insecticidal activity as well as bactericidal activity.

DETAILED DESCRIPTION OF THE EXAMPLES

[0011]The end points and any value in the ranges disclosed in the present invention are not limited to the exact ranges or values; instead, those ranges or values shall be comprehended as encompassing values that are close to those ranges or values. For numeric ranges, the end points of the ranges, the end points of the ranges and the discrete point values, and the discrete point values may be combined to obtain one or more new numeric ranges, which shall be deemed as having been disclosed specifically in this document.

[0012]In a first aspect, the present invention provides a sulfonyl-structure-containing triazinone derivative, which is a compound represented by formula (I a ): wherein R 1< is C1-C12 alkyl, C3-C6 cycloalkyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted benzyl, substituted or unsubstituted phenethyl, substituted or unsubstituted phenylpropyl, substituted or unsubstituted phenylbutyl, nitrogen-containing heterocycle containing 1-10 carbon atoms, oxygen-containing heterocycle containing 1-10 carbon atoms, or sulfur-containing heterocycle containing 1-10 carbon atoms; the substituents of the substituted phenyl, the substituted naphthyl, the substituted benzyl, the substituted phenethyl, the substituted phenylpropyl, and the substituted phenylbutyl are one or more substituents respectively and independently selected from the group consisted of hydroxyl, halogen, cyano, nitro, ester, trifluoromethyl, trifluoromethoxy, amido, C1-C6 alkyl, C1-C6 alkoxy, carbonyloxy substituted by C1-C4 alkyl, and carbonyloxy substituted by C1-C4 alkoxyl.

[0013]According to the present invention, the sulfonyl-structure-containing triazinone derivatives provided in the first aspect and third aspect of the present invention may be generally represented by the following formula (I):

[0014]In the present invention, examples of the C1-C12 alkyl may include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-hendecyl, and n-dodecyl, etc.

[0015]The C1-C6 alkyl and the C1-C4 alkyl may be selected from the above-mentioned examples of alkyls, as long as they meet the corresponding criteria.

[0016]The C1-C6 alkoxy may be an alkoxy formed by an example of alkyl that meets the criterion of 1-6 carbon atoms.

[0017]The examples of the C3-C6 cycloalkyl may be etc., for example.

[0018]The nitrogen-containing heterocycle containing 1-10 carbon atoms may be an unsaturated nitrogen-containing heterocycle or a saturated nitrogen-containing heterocycle, as long as the ring structure of the heterocycle employs nitrogen as a structural atom and the heterocycle has 1-10 carbon atoms. For example, the nitrogen-containing heterocycle containing 1-10 carbon atoms may be selected from the group consisted of unsubstituted pyrrole or pyrrole substituted by C1-C6 alkyl, unsubstituted pyrroline or pyrroline substituted by C1-C6 alkyl, unsubstituted imidazole or imidazole substituted by C1-C7 alkyl, unsubstituted imidazoline or imidazoline substituted by C1-C7 alkyl, unsubstituted pyridine or pyridine substituted by C1-C5 alkyl, unsubstituted pyridinoline or pyridinoline substituted by C1-C5 alkyl, unsubstituted parazole or parazole substituted by C1-C7 alkyl, unsubstituted pyrazolinone or pyrazolinone substituted by C1-C7 alkyl, unsubstituted thiazole or thiazole substituted by C1-C7 alkyl, unsubstituted thiazoline or thiazoline substituted by C1-C7 alkyl, unsubstituted oxazole or oxazole substituted by C1-C7 alkyl, and unsubstituted oxazoline or oxazoline substituted by C1-C7 alkyl, etc. Wherein the alkyl that serves as a substituent may be selected appropriately from the examples of alkyls described above, and the alkyl substitution may be a single-site substitution or a multi-site substitution. There is no particular restriction on the substitution in the present invention.

[0019]The oxygen-containing heterocycle containing 1-10 carbon atoms may be an unsaturated oxygen-containing heterocycle or a saturated oxygen-containing heterocycle, as long as the ring structure of the heterocycle employs oxygen as a structural atom and the heterocycle has 1-10 carbon atoms. For example, the oxygen-containing heterocycle containing 1-10 carbon atoms may be selected from the group consisted of unsubstituted furan or furan substituted by C1-C6 alkyl, unsubstituted tetrahedrafuran or tetrahedrafuran substituted by C1-C6 alkyl, unsubstituted oxazole or oxazole substituted by C1-C7 alkyl, unsubstituted oxazoline or oxazoline substituted by C1-C7 alkyl, unsubstituted 1,3-benzodioxole or 1,3-benzodioxole substituted by C1-C3 alkyl, and unsubstituted 1,4-benzodioxine or 1,4-benzodioxine substituted by C1-C2 alkyl, etc.

[0020]The sulfur-containing heterocycle containing 1-10 carbon atoms may be an unsaturated sulfur-containing heterocycle or a saturated sulfur-containing heterocycle, as long as the ring structure of the heterocycle employs sulfur as a structural atom and the heterocycle has 1-10 carbon atoms. For example, the sulfur-containing heterocycle containing 1-10 carbon atoms may be selected from the group consisted of unsubstituted thiophene or thiophene substituted by C1-C6 alkyl, unsubstituted tetrahedrathiophene or tetrahedrathiophene substituted by C1-C6 alkyl, unsubstituted thiazole or thiazole substituted by C1-C7 alkyl, and unsubstituted thiazoline or thiazoline substituted by C1-C7 alkyl, etc.

[0021]Preferably, R 1< is C1-C8 alkyl, C3-C6 cycloalkyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted benzyl, substituted or unsubstituted phenethyl, substituted or unsubstituted phenylpropyl, substituted or unsubstituted phenylbutyl, nitrogen-containing heterocycle containing 2-8 carbon atoms, oxygen-containing heterocycle containing 2-8 carbon atoms, or sulfur-containing heterocycle containing 2-8 carbon atoms; the substituents of the substituted phenyl, the substituted naphthyl, the substituted benzyl, the substituted phenethyl, the substituted phenylpropyl, and the substituted phenylbutyl are one or more substituents respectively and independently selected from the group consisted of hydroxyl, F, Cl, Br, I, cyano, nitro, -COOCH 3 , -COOCH 2 CH 3 , trifluoromethyl, trifluoromethoxy, -NH-CO-CH 3 , -NH-CO-CH 2 CH 3 , methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, C1-C5 alkyl, C1-C5 alkoxy, -O-CO-CH 3 , -O-CO-CH 2 CH 3 , -O-CO-O-CH 3 , and -O-CO-O-CH 2 CH 3 .

[0022]In a preferred embodiment of the present invention, the compound represented by formula (I a ) is at least one of the compounds represented by the following formulae:

I a -1

I a -2

I a -3

I a -4

I a -5

I a -6

I a -7

I a -8

I a -9

I a -10

I a -11

I a -12

I a -13

I a -14

I a -15

I a -16

I a -17

I a -18

I a -19

I a -20

I a -21

I a -22

I a -23

I a -24

I a -25

I a -26

I a -27

I a -28

I a -29

I a -30

I a -31

I a -32

I a -33

I a -34

[0023]In a second aspect, the present invention provides a preparation method of the above-mentioned triazinone derivative, which comprises: controlling amino-triazinone represented by formula (II) and sulfonyl chloride compound represented by formula (III) to have a substitution reaction in an organic solvent in the presence of an acid binding agent to obtain a compound represented by formula (I a );

[0024]The preparation procedure may be expressed by the following route I: route I:

[0025]According to the present invention, the compound represented by formula (III) may be selected specifically according to the required formula (I a ), and the R 1< in the formula has been described above and will not be further detailed.

[0026]Preferably, the molar ratio of the amino-triazinone represented by formula (II) to the sulfonyl chloride compound represented by formula (III) is 1:0.8-1.2, preferably is 1:1-1.1.

[0027]Preferably, the acid binding agent is at least one of the agents selected from the group consisted of sodium carbonate, potassium carbonate, cesium carbonate, triethylamine, and pyridine.

[0028]The dosage of the acid binding agent may vary within a wide range. For example, the molar ratio of the amino-triazinone represented by formula (II) to the acid binding agent may be 1:0.08-0.5, preferably is 1:0.1-0.3. The pyridine may also be used as the solvent in the above-mentioned method. To that end, when pyridine is used as a solvent, the dose of pyridine is not limited to the dose specified above, as long as the requirement for the dose of the solvent is met.

[0029]Preferably, the organic solvent is at least one of the solvents selected from the group consisted of methanol, ethanol, pyridine, N,N-dimethyl formamide and dimethyl sulfoxide.

[0030]Preferably, the organic solvent is dosed so that the concentration of the amino-triazinone represented by formula (II) is 0.05-0.5 mmol/mL.

[0031]Preferably, the conditions of the substitution reaction include: temperature: 15-40°C (preferably 20-35°C); time: 4-12 h.

[0032]In a third aspect, the present invention provides a sulfonyl-structure-containing triazinone derivative, which is a compound represented by formula (I b ): wherein each R 1< is respectively and independently selected from the group consisted of C1-C2 alkyl, C3-C6 cycloalkyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted benzyl, substituted or unsubstituted phenethyl, substituted or unsubstituted phenylpropyl, substituted or unsubstituted phenylbutyl, nitrogen-containing heterocycle containing 1-10 carbon atoms, oxygen-containing heterocycle containing 1-10 carbon atoms, or sulfur-containing heterocycle containing 1-10 carbon atoms; the substituents of the substituted phenyl, the substituted naphthyl, the substituted benzyl, the substituted phenethyl, the substituted phenylpropyl, and the substituted phenylbutyl are one or more substituents respectively and independently selected from the group consisted of hydroxyl, halogen, cyano, nitro, ester, trifluoromethyl, trifluoromethoxy, amido, C1-C6 alkyl, C1-C6 alkoxy, carbonyloxy substituted by C1-C4 alkyl, and carbonyloxy substituted by C1-C4 alkoxy.

[0033]In an embodiment of the present invention, the R 1< in the present invention may be selected from the group consisted of C1-C12 alkyl, C3-C6 cycloalkyl, phenyl, benzyl, phenethyl, phenylpropyl, phenylbutyl, C1-C10 nitrogen-containing heterocycle, C1-C10 oxygen-containing heterocycle, C1-C10 sulfur-containing heterocycle, or substituted phenyl (wherein the substituent may be hydrogen, hydroxyl, halogen, cyano, nitro, ester, fluorine, trifluoromethyl, trifluoromethoxy, amido, C1-C5 alkyl, C1-C6 alkoxy, C1-C4 alkyl carbonyloxy, or C1-C4 alkoxy carbonyloxy; and may contain 2-3 substituents described above at the same time).

[0034]Wherein the two R 1< in the formula (I b ) may be the same or different, and may be selected respectively and independently; wherein the R 1< in the formula (I b ) may be selected from relevant groups in the formula (I a ) described above, and there is no further restriction on it in the present invention. Preferably, each R 1< is respectively and independently selected from the group consisted of C1-C8 alkyl, C3-C6 cycloalkyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted benzyl, substituted or unsubstituted phenethyl, substituted or unsubstituted phenylpropyl, substituted or unsubstituted phenylbutyl, nitrogen-containing heterocycle containing 2-8 carbon atoms, oxygen-containing heterocycle containing 2-8 carbon atoms, and sulfur-containing heterocycle containing 2-8 carbon atoms; the substituents of the substituted phenyl, the substituted naphthyl, the substituted benzyl, the substituted phenethyl, the substituted phenylpropyl, and the substituted phenylbutyl are one or more substituents respectively and independently selected from the group consisted of hydroxyl, F, Cl, Br, I, cyano, nitro, -COOCH 3 , -COOCH 2 CH 3 , trifluoromethyl, trifluoromethoxy, -NH-CO-CH 3 , -NH-CO-CH 2 CH 3 , methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, C1-C5 alkyl, C1-C5 alkoxy, -O-CO-CH 3 , -O-CO-CH 2 CH 3 , -O-CO-O-CH 3 , and -O-CO-O-CH 2 CH 3 .

[0035]In a preferred embodiment of the present invention, the compound represented by formula (I b ) is at least one of the compounds represented by the following formulae:

I b -1

I b -2

I b -3

I b -4

I b -5

I b -6

I b -7

I b -8

I b -9

[0036]In a fourth aspect, the present invention provides a preparation method of the above-mentioned triazinone derivative, which comprises: controlling amino-triazinone represented by formula (II) and sulfonyl chloride compound represented by formula (III) to have a substitution reaction in an organic solvent in the presence of an acid binding agent to obtain a compound represented by formula (I b );

[0037]The method may be generally summarized as the following route: triazinone (II) reacts with different sulfonyl chlorides to obtain the compound I b ; route II: wherein the compound represented by formula (III) may be specifically selected according to the required formula (I b ), and the R 1< in the formula has been described above, and will not be further detailed here.

[0038]Preferably, the molar ratio of the amino-triazinone represented by formula (II) to the sulfonyl chloride compound represented by formula (III) is 1:1.8-2.5, preferably is 1:2-2.4.

[0039]Preferably, the acid binding agent is at least one of the agents selected from the group consisted of sodium carbonate, potassium carbonate, cesium carbonate, triethylamine, and pyridine.

[0040]The dosage of the acid binding agent may vary within a wide range. For example, the molar ratio of the amino-triazinone represented by formula (II) to the acid binding agent may be 1:0.08-0.5, preferably is 1:0.1-0.3. The pyridine may also be used as the solvent in the above-mentioned method. To that end, when pyridine is used as a solvent, the dose of pyridine is not limited to the dose specified above, as long as the requirement for the dose of the solvent is met.

[0041]Preferably, the organic solvent is at least one of the solvents selected from the group consisted of methanol, ethanol, pyridine, N,N-dimethyl formamide and dimethyl sulfoxide.

[0042]Preferably, the organic solvent is dosed so that the concentration of the amino-triazinone represented by formula (II) is 0.05-0.5 mmol/mL.

[0043]Preferably, the conditions of the substitution reaction include: temperature: 15-40°C (preferably 20-35°C); time: 4-12 h.

[0044]In a fifth aspect, the present invention provides a use of the above-mentioned triazinone derivative in insect killing.

[0045]The triazinone derivatives provided in the present invention have relatively high insecticidal activity, and have relatively high insecticidal activity especially against aphides, mosquito larvae, cotton bollworms, maize borers, and armyworms.

[0046]For the purpose of obtaining relatively high insecticidal activity, preferably, the sulfonyl-structure-containing triazinone derivative in the present invention is at least one of the following compounds:

2-methyl-N-(6-methyl-3-oxo-2,3-dihydro-1,2,4-triazin-4(5H)-yl)benzenesulfonamide (I a -10); 3-methyl-N-(6-methyl-3-oxo-2,3-dihydro-1,2,4-triazin-4(5H)-yl)benzenesulfonamide (I a -11); 4-methyl-N-(6-methyl-3-oxo-2,3-dihydro-1,2,4-triazin-4(5H)-yl)benzenesulfonamide (I a -12); 2,4,6-trimethyl-N-(6-methyl-3-oxo-2,3-dihydro-1,2,4-triazin-4(5H)-yl)benzenesulfonamide (I a -13); 4-methoxy-N-(6-methyl-3-oxo-2,3-dihydro-1,2,4-triazin-4(5H)-yl)benzenesulfonamide (I a -14); 4-tert-butyl-N-(6-methyl-3-oxo-2,3-dihydro-1,2,4-triazin-4(5H)-yl)benzenesulfonamide (I a -15); 4-bromo-N-(6-methyl-3-oxo-2,3-dihydro-1,2,4-triazin-4(5H)-yl)benzenesulfonamide (I a -22).

[0047]Particularly, the sulfonyl-structure-containing triazinone derivatives in the present invention exhibit outstanding insecticidal activity against aphides, wherein the compounds I a -10, I a -11, I a -12, I a -13, I a -14 and I a -15 exhibit insecticidal activity with mortalities of 25%, 15%, 30%, 10%, 35%, and 10% respectively at a concentration of 2.5 mg/kg, while pymetrozine has no insecticidal activity at the same concentration. Besides, some of the compounds exhibit satisfactory insecticidal activity against mosquito larvae, wherein at a concentration of 1 mg/kg, the compounds I a -19, I a -23 and I a -26 exhibit insecticidal activity with mortalities of 60%, 30% and 20% against mosquito larvae; especially, the compound I a -22 exhibits insecticidal activity with a mortality of 40% against mosquito larvae at a concentration of 0.5 mg/kg. In addition, all of the compounds exhibit insecticidal activity against cotton bollworms, maize borers, and armyworms.

[0048]The present invention further provides an insecticidal method that utilizes the above-mentioned triazinone derivative as an insecticide.

[0049]In a sixth aspect, the present invention provides a use of the above-mentioned triazinone derivative in bacterium killing.

[0050]The triazinone derivatives provided in the present invention have high insecticidal activity, especially against at least one of the pathogenic bacteria that may cause tomato early blight, wheat head blight, potato late blight, capsicum phytophthora blight, sclerotinia rot of colza, cucumber gray mold, rice sheath blight, cucumber fusarium wilt, cercospora brown spot of peanut, apple ring rot, wheat sheath blight, corn southern leaf blight, watermelon anthracnose, and rice bakanae disease.

[0051]For the purpose of obtaining higher bactericidal activity, preferably, the sulfonyl-structure-containing triazinone derivative in the present invention is at least one of the following compounds: 2-methyl-N-(6-methyl-3-oxo-2,3-dihydro-1,2,4-triazin-4(5H)-yl)benzenesulfonamide (I a -10); 3-methyl-N-(6-methyl-3-oxo-2,3-dihydro-1,2,4-triazin-4(5H)-yl)benzenesulfonamide (I a -11); 4-methyl-N-(6-methyl-3-oxo-2,3-dihydro-1,2,4-triazin-4(5H)-yl)benzenesulfonamide (I a- 12); 2,4,6-trimethyl-N-(6-methyl-3-oxo-2,3-dihydro-1,2,4-triazin-4(5H)-yl)benzenesulfonamide (I a -13); 4-methoxy-N-(6-methyl-3-oxo-2,3-dihydro-1,2,4-triazin-4(5H)-yl)benzenesulfonamide (I a -14); 4-tert-butyl-N-(6-methyl-3-oxo-2,3-dihydro-1,2,4-triazin-4(5H)-yl)benzenesulfonamide (I a -15); 4-bromo-N-(6-methyl-3-oxo-2,3-dihydro-1,2,4-triazin-4(5H)-yl)benzenesulfonamide (I a -22). Wherein especially the compounds I a -4, I a -12 and I b -5 exhibit outstanding bactericidal activity against a variety of pathogenic bacteria at a concentration of 50 mg/kg.

[0052]The present invention further provides a bactericidal method that utilizes the above-mentioned triazinone derivative as a bactericide.

[0053]The following examples and biological test results can be used to further illustrate the present invention, but not mean to constitute any limitation to the present invention.

Example 1:

(1) Synthesis of N-(6-methyl-3-oxo-2,3-dihydro-1,2,4-triazin-4(5H)-yl)-methylsulfonylamide (Ia-1)

[0054]

[0055]Amino-triazinone (0.26g, 2mmol, from TCI (Shanghai) Development Co., Ltd.) and pyridine (20mL) are added into a 100mL single-neck flask and stirred to dissolve, then methylsulfonyl chloride (0.24g, 2.1mmol, from Energy Chemical Co., Ltd.) is added into the flask, and the mixture is stirred and held overnight at room temperature, the reaction is monitored with a TLC till it is finished. After desolvation of the reaction liquid under reduced pressure, water is added to the mixture and the product is extracted with methylene chloride and then washed twice with saturated sodium chloride solution and dried with sodium sulfate; next, the product is treated by chromatography in a silica-gel column with methylene chloride/methanol (150:1-100:1); thus, 0.32g white solid is obtained, the yield is 78%, and the melting point of the white solid is 191-192°C. 1< H NMR (300 MHz, DMSO-d 6 ) δ 10.00 (s, 1H, NH), 9.83 (s, 1H, NH), 4.15 (s, 2H, CH 2 ), 3.01 (s, 3H, CH 3 ), 1.86 (s, 3H, CH 3 ); 13< C NMR (100 MHz, DMSO-d 6 ) δ 151.4, 146.0, 53.9, 41.1, 20.1. ESI-HRMS(m/z): Calcd. for C 5 H 11 N 4 O 3 S [M+H] +< 207.0546; found 207.0548.

(2) Synthesis of compounds I a -2∼I a -34 by repeating the steps for I a -1

[0056]Except:

In the preparation of the compound I a -2, the methylsulfonyl chloride is replaced with ethylsulfonyl chloride (from Energy Chemical Co., Ltd.) in the same molar mass; In the preparation of the compound I a -3, the methylsulfonyl chloride is replaced with n-propylsulfonyl chloride (from Beijing Innochem Science & Technology Co., Ltd.) in the same molar mass; In the preparation of the compound I a -4, the methylsulfonyl chloride is replaced with n-butylsulfonyl chloride (from Beijing Innochem Science & Technology Co., Ltd.) in the same molar mass; In the preparation of the compound I a -5, the methylsulfonyl chloride is replaced with (from Beijing Innochem Science & Technology Co., Ltd.) in the same molar mass; In the preparation of the compound I a -6, the methylsulfonyl chloride is replaced with (from Beijing Innochem Science & Technology Co., Ltd.) in the same molar mass; In the preparation of the compound I a -7, the methylsulfonyl chloride is replaced with (from Tianjin Heowns Biochemical Technology Co., Ltd.) in the same molar mass; In the preparation of the compound I a -8, the methylsulfonyl chloride is replaced with (from J&K Scientific Ltd.) in the same molar mass; In the preparation of the compound I a -9, the methylsulfonyl chloride is replaced with (from Tianjin Reagents Co., Ltd.) in the same molar mass; In the preparation of the compound I a -10, the methylsulfonyl chloride is replaced with (from Energy Chemical Co., Ltd.) in the same molar mass; In the preparation of the compound I a -11, the methylsulfonyl chloride is replaced with (from Shanghai Boka Chemical Technology Co., Ltd.) in the same molar mass; In the preparation of the compound I a -12, the methylsulfonyl chloride is replaced with (from Shanghai Aladdin Bio-Chem Technology Co., LTD) in the same molar mass; In the preparation of the compound I a -13, the methylsulfonyl chloride is replaced with (from Energy Chemical Co., Ltd.) in the same molar mass; In the preparation of the compound I a -14, the methylsulfonyl chloride is replaced with (from Shanghai Aladdin Bio-Chem Technology Co., LTD) in the same molar mass; In the preparation of the compound I a -15, the methylsulfonyl chloride is replaced with (from Energy Chemical Co., Ltd.) in the same molar mass; In the preparation of the compound I a -16, the methylsulfonyl chloride is replaced with (from Shanghai Boka Chemical Technology Co., Ltd.) in the same molar mass; In the preparation of the compound I a -17, the methylsulfonyl chloride is replaced with (from Shanghai Boka Chemical Technology Co., Ltd.) in the same molar mass; In the preparation of the compound I a -18, the methylsulfonyl chloride is replaced with (from Shanghai Boka Chemical Technology Co., Ltd.) in the same molar mass; In the preparation of the compound I a -19, the methylsulfonyl chloride is replaced with (from Shanghai Boka Chemical Technology Co., Ltd.) in the same molar mass; In the preparation of the compound I a -20, the methylsulfonyl chloride is replaced with (from Beijing Innochem Science & Technology Co., Ltd.) in the same molar mass; In the preparation of the compound I a -21, the methylsulfonyl chloride is replaced with (from Tianjin Heowns Biochemical Technology Co., Ltd.) in the same molar mass; In the preparation of the compound I a -22, the methylsulfonyl chloride is replaced with (from Tianjin Heowns Biochemical Technology Co., Ltd.) in the same molar mass; In the preparation of the compound I a -23, the methylsulfonyl chloride is replaced with (from Shanghai Boka Chemical Technology Co., Ltd.) in the same molar mass; In the preparation of the compound I a -24, the methylsulfonyl chloride is replaced with (from Shanghai Boka Chemical Technology Co., Ltd.) in the same molar mass; In the preparation of the compound I a -25, the methylsulfonyl chloride is replaced with (from Shanghai Boka Chemical Technology Co., Ltd.) in the same molar mass; In the preparation of the compound I a -26, the methylsulfonyl chloride is replaced with (from Shanghai Boka Chemical Technology Co., Ltd.) in the same molar mass; In the preparation of the compound I a -27, the methylsulfonyl chloride is replaced with (from Shanghai Boka Chemical Technology Co., Ltd.) in the same molar mass; In the preparation of the compound I a -28, the methylsulfonyl chloride is replaced with (from Energy Chemical Co., Ltd.) in the same molar mass; In the preparation of the compound I a -29, the methylsulfonyl chloride is replaced with (from Energy Chemical Co., Ltd.) in the same molar mass; In the preparation of the compound I a -30, the methylsulfonyl chloride is replaced with (from Energy Chemical Co., Ltd.) in the same molar mass; In the preparation of the compound I a -31, the methylsulfonyl chloride is replaced with (from Energy Chemical Co., Ltd.) in the same molar mass; In the preparation of the compound I a -32, the methylsulfonyl chloride is replaced with (from Energy Chemical Co., Ltd.) in the same molar mass; In the preparation of the compound I a -33, the methylsulfonyl chloride is replaced with (from Beijing Innochem Science & Technology Co., Ltd.) in the same molar mass; In the preparation of the compound I a -34, the methylsulfonyl chloride is replaced with (from Beijing Innochem Science & Technology Co., Ltd.) in the same molar mass;

[0057]The obtained compounds are characterized as follows:

N-(6-methyl-3-oxo-2,3-dihydro-1,2,4-triazin-4(5H)-yl)-ethylsulfonamide (I a -2) White solid, yield 76%, melting point 206-208°C. 1< H NMR (300 MHz, DMSO-d 6 ) δ 9.98 (s, 1H, NH), 9.79 (s, 1H, NH), 4.15 (s, 2H, CH 2 ), 3.10 (q, J = 7.2 Hz, 2H, CH 2 CH 3 ), 1.85 (s, 3H, CH 3 ), 1.27 (t, J = 7.2 Hz, 3H, CH 2 CH 3 ); 13< C NMR (100 MHz, DMSO-d 6 ) δ 151.2, 145.7, 53.8, 46.7, 19.8, 7.9. ESI-HRMS(m/z): Calcd. for C 6 H 13 N 4 O 3 S [M+H] +< 221.0703; found 221.0701. N-(6-methyl-3-oxo-2,3-dihydro-1,2,4-triazin-4(5H)-yl)-n-propylsulfonamide (I a -3) White solid, yield is 73%, melting point is 177-178°C. 1< H NMR (300 MHz, DMSO-d 6 ) δ 9.98 (s, 1H, NH), 9.81 (s, 1H, NH), 4.15 (s, 2H, CH 2 ), 3.07 (t, J = 7.5 Hz,2H, CH 2 CH 2 CH 3 ), 1.85 (s, 3H, CH 3 ), 1.73-1.80 (m, 2H, CH 2 CH 2 CH 3 ), 0.95 (t, J = 7.5 Hz, 3H, CH 2 CH 2 CH 3 ); 13< C NMR (100 MHz, DMSO-d 6 ) δ 151.2, 145.6, 53.8, 19.8, 16.7, 12.8. ESI-HR

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